CN116875310A - Red light emission silicon-based rare earth composite nano fluorescent powder and preparation method thereof - Google Patents
Red light emission silicon-based rare earth composite nano fluorescent powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 37
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 30
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 86
- 239000000243 solution Substances 0.000 claims description 67
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000295 emission spectrum Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
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- 239000000523 sample Substances 0.000 description 3
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- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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Abstract
The application discloses a preparation method of a red light emission silicon-based rare earth composite nano fluorescent powder. Uses the hollow silicon dioxide sphere HHSS-OH with activated surface hydroxyl as a carrier, and uses the surface hydroxyl and LaVO thereof 4 :Eu 3+ Coordination of LaVO 4 :Eu 3+ The nano particles are anchored on the surface of HHSS, and HHSS@LaVO is obtained after annealing 4 :Eu 3+ Composite nano fluorescent powder; the LaVO 4 :Eu 3+ Is Eu 3+ Doped LaVO 4 Within the lattice. The application prepares HHSS@LaVO 4 :Eu 3+ The composite nano fluorescent powder has the advantages of simple preparation method, low cost and the like, and the obtained HHSS@LaVO 4 :Eu 3+ The composite nano fluorescent powder has strong down-conversion red light emission, and is compatible with LaVO 4 ：Eu 3+ HHSS@LaVO compared with the solution 4 :Eu 3+ The fluorescence intensity of the colloid solution is improved by 5 times.
Description
Technical Field
The application relates to a preparation method of nano fluorescent powder, in particular to a preparation method of red light emission silicon-based rare earth composite nano fluorescent powder.
Background
The rare earth is taken as non-renewable resource, and the improvement of the effective utilization of the rare earth fluorescent material is a problem to be solved urgently. One well-established design strategy is to reduce the size of rare earth doped luminescent materials, form stable colloidal solutions and enhance fluorescence to enable new applications such as ion sensing and biomarkers. Initially, researchers produced phosphors with a minimum size of several hundred nanometers by ball milling of bulk phosphors, which prevented their widespread use. Therefore, the development of high-quality small-size nanocrystals is favored by researchers because of their wide application prospects. To date, new manufacturing methods to produce nanocrystals with high fluorescence intensity (less than 100nm in size) have stimulated the development of this field, however, the severe agglomeration of small-sized fluorescent nanocrystals still has affected their widespread use.
Thus, researchers have proposed a promising strategy to inhibit agglomeration: the rare earth is vectorized to form the composite luminescent material, which not only improves and expands the luminescent characteristic of the nano particles and increases the solution stability, but also is beneficial to the functional application thereof. In recent years, various rare earth composite fluorescent materials have been favored by researchers. Some researchers have incorporated rare earth ions into organics or MOFs. Other studies reported the incorporation of rare earths into inorganic supports via organic ligands. In particular, siO 2 Inorganic carrier with nano particles as best rare earth luminophoreOne is that it has the characteristics of good light transmittance, large specific surface area, low density, good biocompatibility, easy formation of colloid solution, etc. However, the preparation process of the silicon-based rare earth composite fluorescent material reported at present is complex, and the optical performance of the silicon-based rare earth composite fluorescent material is not improved or even weakened.
In order to solve the technical problems, the application provides a preparation method of a red light emission silicon-based rare earth composite nano fluorescent powder.
Disclosure of Invention
The application aims to provide a preparation method of red light emission silicon-based rare earth composite nano fluorescent powder. The application has HHSS@LaVO 4 :Eu 3+ The composite nano fluorescent powder has strong down-conversion red light emission, and is compatible with LaVO 4 ：Eu 3+ HHSS@LaVO compared with the solution 4 ：Eu 3+ The fluorescence intensity of the colloidal solution is improved by 5 times. The prepared fluorescent powder has the advantages of fluorescence enhancement, good biocompatibility, no toxicity, low cost and the like, and the material has good application prospects in the fields of fluorescence anti-counterfeiting, ion sensing, fluorescent probes and the like.
The technical scheme of the application is as follows: a red light emitting silicon-based rare earth composite nano fluorescent powder uses hollow silicon dioxide sphere HHSS-OH with surface hydroxyl activated as a carrier, and uses the surface hydroxyl and LaVO thereof 4 :Eu 3+ Coordination of LaVO 4 :Eu 3+ The nano particles are anchored on the surface of HHSS, and HHSS@LaVO is obtained after annealing 4 :Eu 3+ Composite nano fluorescent powder; the LaVO 4 :Eu 3+ Is Eu 3+ Doped LaVO 4 Within the lattice.
In the red light emitting silicon-based rare earth composite nano fluorescent powder, hollow silica spheres HHSS-OH and LaVO with surface hydroxyl groups activated are prepared 4 :Eu 3+ Mixing the precursor solutions, stirring to form a suspension, performing hydrothermal reaction, centrifuging to collect solid, drying, and annealing to obtain HHSS@LaVO 4 :Eu 3+ Composite nano fluorescent powder; the LaVO 4 :Eu 3+ La (NO) 3 ) 3 ·6H 2 O、Eu(NO 3 ) 3 ·6H 2 O and NH 4 VO 3 Is prepared by the method.
In the red light emission silicon-based rare earth composite nano fluorescent powder, the silicon dioxide spheres are refluxed and stirred in the mixed solution of hydrochloric acid and ethanol to remove CTAB templates, so that the hollow silicon dioxide sphere HHSS-OH with surface hydroxyl activation is obtained.
The preparation method of the red light emission silicon-based rare earth composite nano fluorescent powder comprises the following steps:
(1) Adding silicon dioxide balls into absolute ethyl alcohol, adding hydrochloric acid solution after ultrasonic stirring, refluxing and stirring under the oil bath condition, cooling, filtering and washing, collecting solid, and drying to obtain HHSS-OH with surface hydroxyl activation as a product A;
(2) Adding the product A into absolute ethyl alcohol, ultrasonically stirring, adding deionized water, and ultrasonically stirring again to obtain milky suspension, wherein the milky suspension is the product B;
(3) La (NO) 3 ) 3 ·6H 2 Adding O into deionized water, stirring, and adding Eu (NO) 3 ) 3 ·6H 2 O, stirring to obtain a transparent La-Eu solution which is a C product;
(4) NH is added to 4 VO 3 Adding into deionized water, heating, stirring, dissolving, and cooling to room temperature to obtain NH 4 VO 3 The solution is D;
(5) Adding the product C into the product B, ultrasonically stirring, adding the product D, and continuously ultrasonically stirring to obtain a mixed solution which is the product E;
(6) Carrying out hydrothermal reaction on the E product, cooling, filtering, washing, collecting solid, drying and annealing to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
In the step (1), 0.8-1.2g of silicon dioxide balls are added into 100-140mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 20-40min, 220-260 mu L of hydrochloric acid solution is added, the mass fraction of the hydrochloric acid solution is 36-38%, reflux stirring is carried out for 4-6h under the oil bath condition of 70-90 ℃, cooling is carried out to 20-30 ℃, filtering and washing are carried out, solid is collected, and drying is carried out for 8-12h at 70-90 ℃, thus obtaining the hollow silicon dioxide HHSS-OH with surface hydroxyl activation, which is A product.
In the step (2), 0.3-0.5g of A product is added into 4-8mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 20-40min, 30-38mL of deionized water is added, ultrasonic stirring is carried out for 4-6h, and suspension is obtained as B product.
In the preparation method of the red light emitting silicon-based rare earth composite nano fluorescent powder, in the step (3), 0.10 to 0.15. 0.15gLa (NO 3 ) 3 ·6H 2 Adding O into 15-25mL deionized water, stirring, and adding 0.01-0.02-gEu (NO) 3 ) 3 ·6H 2 And O, stirring to obtain La-Eu solution which is a C product.
In the preparation method of the red light emitting silicon-based rare earth composite nano fluorescent powder, in the step (4), the ratio of 0.03 to 0.05 to gNH is set 4 VO 3 Adding into 15-25mL deionized water, heating at 50-70deg.C, stirring for dissolving, and cooling to 20-30deg.C to obtain NH 4 VO 3 The solution is D product.
In the preparation method of the red light emitting silicon-based rare earth composite nano fluorescent powder, in the step (5), 15-20mLC products are added into 34-46mLB products, ultrasonic stirring is carried out for 20-40min, 15-25mLD products are added into the mixture, ultrasonic stirring is continued for 20-40min, and the mixture is E products.
In the step (6), the E product is subjected to hydrothermal reaction at 100-120 ℃ for 10-12 hours, cooled to 15-30 ℃, filtered, washed, collected into solid, dried at 70-90 ℃ for 8-12 hours, heated to 700-900 ℃ at a heating rate of 4-10 ℃/min, baked for 5-7 hours, naturally cooled, and finally HHSS@LaVO is obtained 4 :Eu 3+ And (3) compounding nano fluorescent powder.
Compared with the prior art, the application has the following beneficial effects:
the application disperses silica spheres in a mixed solution of hydrochloric acid and ethanol, and the mixture is stirred and refluxed at 80 ℃ to dissolve CTAB in the silica spheres into the mixed solution and obtain hollow silica spheres HHSS-OH with activated surface hydroxyl groups. Hollow silicon dioxide HHSS-OH has special big sphere@small sphere composite nano level hollowThe cavity structure, the average grain diameter of the big hollow sphere is about 100nm, the sphere wall is formed by stacking small hollow spheres with the grain diameter of 8-15nm, and the specific surface area is as high as 597.21m 2 And/g. The surface hydroxyl has coordination capability, which is favorable for LaVO 4 :Eu 3+ The nanoparticles are anchored to the HHSS surface. HHSS-OH was mixed with ethanol and water and stirred ultrasonically to give a white suspension, which was then combined with La (NO) 3 ) 3 ·6H 2 O、Eu(NO 3 ) 3 ·6H 2 O and NH 4 VO 3 LaVO obtained by the reaction 4 :Eu 3+ Mixing and ultrasonic stirring the precursor solution, performing hydrothermal reaction, and utilizing the high-temperature and high-pressure conditions in the reaction kettle and the mass transfer effect of gas phase-solid phase to enable LaVO on the HHSS surface 4 :Eu 3+ The nanoparticles are recrystallized. LaVO with HHSS surface increased by annealing 4 :Eu 3+ The crystallinity of the nanoparticle, in turn, increases its fluorescence intensity. The HHSS@LaVO obtained after annealing is carried out due to the supporting and dispersing effects of the HHSS-OH carrier 4 :Eu 3+ LaVO in composite nano fluorescent powder 4 :Eu 3+ The average size of the nano particles is about 2nm, and the nano particles are uniformly dispersed on the surface of HHSS, so that large particles are not agglomerated. The obtained HSS@LaVO 4 :Eu 3+ The composite nano fluorescent powder shows strong down-conversion red light emission (the main emission peak position is 618 nm) under the excitation of ultraviolet light of 298 nm. In addition, since HHSS@LaVO was obtained 4 :Eu 3+ The average grain diameter of the composite nano fluorescent powder is about 100nm, and the unique nano-level cavity structure of HHSS is maintained, so that stable luminous colloid solution is easy to form. And LaVO 4 :Eu 3+ HSS@LaVO compared with the solution (8 mg/L) with the same concentration 4 :Eu 3+ The fluorescence intensity of the colloidal solution is enhanced by 5 times, and the colloidal solution has strong stability.
In conclusion, the application prepares HHSS@LaVO 4 :Eu 3+ The composite nano fluorescent powder has the advantages of simple preparation method, low cost and the like, and the obtained HHSS@LaVO 4 :Eu 3+ The composite nano fluorescent powder has strong down-conversion red light emission, and is compatible with LaVO 4 ：Eu 3+ HHSS@LaVO compared with the solution 4 :Eu 3+ Fluorescence intensity of colloidal solutionThe degree is improved by 5 times.
Drawings
FIG. 1 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ HHSS-OH and LaVO prepared by composite nano fluorescent powder and comparative example 4 :Eu 3+ An XRD pattern of (a);
FIG. 2 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ HHSS-OH and LaVO prepared by composite nano fluorescent powder and comparative example 4 :Eu 3+ Is a FTIR spectrum of (C);
FIG. 3 shows (c) HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Composite nano fluorescent powder and (a) HHSS-OH and (b) LaVO prepared by comparative example 4 :Eu 3+ SEM images of (2);
FIG. 4 shows (c) HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Composite nano fluorescent powder and (a) HHSS-OH and (b) LaVO prepared by comparative example 4 :Eu 3+ HRTEM images of (a);
FIG. 5 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Composite nano fluorescent powder and HHSS-OH N prepared by comparative example 2 Adsorption-desorption isotherms;
FIG. 6 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Excitation-emission spectrum of the composite nano fluorescent powder;
FIG. 7 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Dispersing the composite nano fluorescent powder in an aqueous solution to form emission spectra of colloidal solutions with different concentrations;
FIG. 8 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ An emission spectrum of a colloidal solution (20 mg/L) formed by dispersing the composite nano fluorescent powder in an aqueous solution;
FIG. 9 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ The stability test emission spectrum of a colloidal solution (20 mg/L) formed by dispersing the composite nano fluorescent powder in an aqueous solution;
FIG. 10 shows HHSS@LaVO prepared in example 3 and comparative example of the present application 4 :Eu 3+ Composite nano fluorescent powder and LaVO 4 :Eu 3+ Emission spectrum of a solution formed by dispersing the phosphor in an aqueous solution.
Detailed Description
The application is further illustrated by the following figures and examples, which are not intended to be limiting.
Embodiment 1, a method for preparing a red light emission silicon-based rare earth composite nano fluorescent powder, comprising the following steps:
in the step (1), 0.8g of silica spheres is added into 100mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 20min, 220 mu L of hydrochloric acid solution is added, the mass fraction of the hydrochloric acid solution is 36-38%, reflux stirring is carried out for 4h under the condition of 70 ℃ oil bath, cooling is carried out to 20 ℃, filtering and washing are carried out, solid is collected, drying is carried out for 8h under 70 ℃, and hollow silica HHSS-OH with surface hydroxyl activation is obtained as A product;
in the step (2), adding 0.3g of A product into 4mL of absolute ethyl alcohol, ultrasonically stirring for 20min, adding 30mL of deionized water, and ultrasonically stirring for 4h to obtain a suspension, namely B product;
in the step (3), 0.10. 0.10gLa (NO 3 ) 3 ·6H 2 O was added to 15mL of deionized water, stirred, and then added with 0.01. 0.01gEu (NO 3 ) 3 ·6H 2 O, stirring to obtain La-Eu solution which is a C product;
in the step (4), 0.03 and gNH are added 4 VO 3 Adding into 15mL deionized water, heating at 60deg.C, stirring for dissolving, and cooling to 20deg.C to obtain NH 4 VO 3 The solution is D;
in the step (5), adding 15mLC products into 34mLB products, ultrasonically stirring for 20min, adding 15mLD products into the mixture, and continuously ultrasonically stirring for 20min to obtain a mixed solution which is E products;
in the step (6), the E product is subjected to hydrothermal reaction at 100 ℃ for 10 hours, cooled to 15 ℃, filtered, washed, collected into solid, dried at 70 ℃ for 8 hours, and annealed by heating to 700 ℃ at a heating rate of 4 ℃/min for 5 hours and naturally cooled to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
Embodiment 2, a method for preparing red light emission silicon-based rare earth composite nano fluorescent powder, comprises the following steps:
in the step (1), 0.9g of silicon dioxide balls are added into 110mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 25min, 230 mu L of hydrochloric acid solution is added, the mass fraction of the hydrochloric acid solution is 36-38%, reflux stirring is carried out for 4.5h under the condition of 75 ℃ oil bath, cooling is carried out to 25 ℃, filtering and washing are carried out, solid is collected, drying is carried out for 9h under 75 ℃, and hollow silicon dioxide HHSS-OH with surface hydroxyl activation is obtained as a product A;
in the step (2), 0.35g of A product is added into 5mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 25min, 32mL of deionized water is added, ultrasonic stirring is carried out for 4.5h, and suspension liquid is obtained as B product;
in the step (3), 0.12. 0.12gLa (NO 3 ) 3 ·6H 2 O was added to 18mL of deionized water, stirred, and then added with 0.011gEu (NO 3 ) 3 ·6H 2 O, stirring to obtain La-Eu solution which is a C product;
in the step (4), 0.035 to 0.035gNH 4 VO 3 Adding into 18mL deionized water, heating at 55deg.C, stirring for dissolving, cooling to 25deg.C to obtain NH 4 VO 3 The solution is D;
in the step (5), adding 18 pieces mLC into 37mLB pieces, ultrasonically stirring for 25min, adding 18 pieces mLD into the mixture, and continuously ultrasonically stirring for 25min to obtain a mixed solution which is E pieces;
in the step (6), the E product is subjected to hydrothermal reaction at 95 ℃ for 10 hours, cooled to 25 ℃, filtered, washed, collected into solid, dried at 75 ℃ for 9 hours, and annealed by heating to 750 ℃ at a heating rate of 5 ℃/min for 5.5 hours and naturally cooled to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
Embodiment 3, a method for preparing a red light emission silicon-based rare earth composite nano fluorescent powder, comprises the following steps:
in the step (1), 1.0g of silicon dioxide balls are added into 120mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 30min, 240 mu L of hydrochloric acid solution with the mass fraction of 36-38% is added, reflux stirring is carried out for 5h under the condition of 80 ℃ oil bath, cooling is carried out to 25 ℃, filtering and washing are carried out, solid is collected, drying is carried out for 10h under 80 ℃, and hollow silicon dioxide HHSS-OH with surface hydroxyl activation is obtained as A product;
in the step (2), adding 0.4g of A product into 6mL of absolute ethyl alcohol, ultrasonically stirring for 30min, adding 34mL of deionized water, and ultrasonically stirring for 5h to obtain a suspension, namely B product;
in the step (3), 0.13. 0.13gLa (NO 3 ) 3 ·6H 2 O was added to 20mL of deionized water, stirred, and then added with 0.012gEu (NO 3 ) 3 ·6H 2 O, stirring to obtain La-Eu solution which is a C product;
in the step (4), 0.04 to 0.04gNH 4 VO 3 Adding into 20mL deionized water, heating at 60deg.C, stirring for dissolving, and cooling to 25deg.C to obtain NH 4 VO 3 The solution is D;
in the step (5), adding 20mLC products into 40mLB products, ultrasonically stirring for 30min, adding 20mLD products into the mixture, and continuously ultrasonically stirring for 30min to obtain a mixed solution which is E products;
in the step (6), the E product is subjected to hydrothermal reaction at 100 ℃ for 10 hours, cooled to 25 ℃, filtered, washed, collected into solid, dried at 80 ℃ for 10 hours, and annealed by heating to 800 ℃ at a heating rate of 5 ℃/min for 6 hours and naturally cooled to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
Embodiment 4, a method for preparing red light emission silicon-based rare earth composite nano fluorescent powder, comprises the following steps:
in the step (1), 1.1g of silicon dioxide balls are added into 130mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 35min, 250 mu L of hydrochloric acid solution with the mass fraction of 36-38% is added, reflux stirring is carried out for 5.5h under the oil bath condition of 85 ℃, cooling is carried out to 28 ℃, filtering and washing are carried out, solid is collected, drying is carried out for 11h under 85 ℃, and hollow silicon dioxide HHSS-OH with surface hydroxyl activation is obtained as a product A;
in the step (2), 0.45g of A product is added into 7mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 35min, 36mL of deionized water is added, ultrasonic stirring is carried out for 5.5h, and suspension liquid is obtained as B product;
in the step (3), 0.14. 0.14gLa (NO 3 ) 3 ·6H 2 O is added into 23mL of deionized water, stirred, and then0.015. 0.015gEu (NO) 3 ) 3 ·6H 2 O, stirring to obtain La-Eu solution which is a C product;
in the step (4), 0.045 and gNH are added 4 VO 3 Adding into 23mL deionized water, heating at 65deg.C, stirring for dissolving, cooling to 28deg.C to obtain NH 4 VO 3 The solution is D;
in the step (5), adding 23mLC products into 43mLB products, ultrasonically stirring for 35min, adding 23mLD products into the mixture, and continuously ultrasonically stirring for 35min to obtain a mixed solution which is E products;
in the step (6), the E product is subjected to hydrothermal reaction at 105 ℃ for 11 hours, cooled to 28 ℃, filtered, washed, collected into solid, dried at 85 ℃ for 11 hours, and annealed by heating to 850 ℃ at a heating rate of 8 ℃/min for 6.5 hours and naturally cooled to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
Embodiment 5, a method for preparing a red light emitting silicon-based rare earth composite nano fluorescent powder, comprising the following steps:
in the step (1), 1.2g of silicon dioxide balls are added into 140mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 40min, 260 mu L of hydrochloric acid solution with the mass fraction of 36-38% is added, reflux stirring is carried out for 6h under the condition of 90 ℃ oil bath, cooling is carried out to 30 ℃, filtering and washing are carried out, solid is collected, drying is carried out for 12h under the 90 ℃, and hollow silicon dioxide HHSS-OH with surface hydroxyl activation is obtained as A product;
in the step (2), 0.5g of A product is added into 8mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 40min, 38mL of deionized water is added, ultrasonic stirring is carried out for 6h, and suspension liquid is obtained as B product;
in the step (3), 0.15. 0.15gLa (NO 3 ) 3 ·6H 2 O was added to 25mL of deionized water, stirred, and then added with 0.02. 0.02gEu (NO 3 ) 3 ·6H 2 O, stirring to obtain La-Eu solution which is a C product;
in the step (4), 0.05 to 0.05gNH 4 VO 3 Adding into 25mL deionized water, heating at 70deg.C, stirring for dissolving, and cooling to 30deg.C to obtain NH 4 VO 3 The solution is D;
in the step (5), 25mLC products are added into 46mLB products, ultrasonic stirring is carried out for 40min, 25mLD products are added into the mixture, ultrasonic stirring is continued for 40min, and mixed liquid which is E products is obtained;
in the step (6), the E product is subjected to hydrothermal reaction at 110 ℃ for 12 hours, cooled to 30 ℃, filtered, washed, collected into solid, dried at 90 ℃ for 12 hours, and the annealing process is that the E product is heated to 900 ℃ at a heating rate of 10 ℃/min, baked for 7 hours and naturally cooled to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
Comparative example 1 LaVO 4 :Eu 3+ Preparing fluorescent powder:
will be 0.13gLa (NO 3 ) 3 ·6H 2 O was added to 20mL of deionized water, stirred, and then added with 0.012gEu (NO 3 ) 3 ·6H 2 O, stirring to obtain La-Eu solution;
will be 0.04gNH 4 VO 3 Adding into 20mL deionized water, heating at 60deg.C, stirring for dissolving, and cooling to 25deg.C to obtain NH 4 VO 3 A solution;
adding La-Eu solution to NH 4 VO 3 Stirring the solution for 20 to 40 minutes by ultrasonic, adding NaOH solution (2M) to adjust the pH value of the mixed solution to be 3 to 4, and continuously stirring the mixed solution for 30 minutes to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution at 100 ℃ for 10 hours, cooling to 25 ℃, filtering, washing, collecting solids, drying at 80 ℃ for 10 hours, heating to 800 ℃ at a heating rate of 5 ℃/min in an annealing process, roasting for 6 hours, and naturally cooling to obtain LaVO 4 :Eu 3+ Fluorescent powder.
Comparative example 2 preparation of surface hydroxyl activated hollow silica HHSS-OH:
adding 1.0g of silica spheres into 120mL of absolute ethyl alcohol, stirring for 20-40min by ultrasonic, adding 240 mu L of hydrochloric acid solution with the mass fraction of 36-38%, refluxing and stirring for 5h under the oil bath condition of 80 ℃, cooling to 25 ℃, filtering and washing, collecting solid, and drying at 80 ℃ for 10h to obtain the hollow silica HHSS-OH with surface hydroxyl activation.
Experimental data:
for HHSS@LaVO prepared by the preparation method of example 4 :Eu 3+ LaVO prepared by composite nano fluorescent powder and comparative example 4 :Eu 3+ The phosphor and HHSS-OH were characterized as follows:
FIG. 1 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ HHSS-OH and LaVO prepared by composite nano fluorescent powder and comparative example 4 :Eu 3+ Is a XRD pattern of (C). As can be seen from the figure, HHSS-OH and HHSS@LaVO 4 :Eu 3+ The wide diffraction peak of the diffraction spectrum of the fluorescent powder in the range of 2θ=18 to 28 degrees belongs to amorphous silicon, laVO 4 :Eu 3+ And HHSS@LaVO 4 :Eu 3+ Diffraction peak of composite nano fluorescent powder and tetragonal LaVO 4 Corresponds to the standard card (JCPDS, no. 32-0504). HHSS@LaVO 4 :Eu 3+ LaVO in composite nano fluorescent powder 4 :Eu 3+ Is weaker, indicating LaVO 4 :Eu 3+ The nanoparticles are uniformly dispersed on the HHSS surface.
FIG. 2 shows HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ HHSS-OH and LaVO prepared by composite nano fluorescent powder and comparative example 4 :Eu 3+ Is a FTIR spectrum of (C). FTIR spectrum of HHSS-OH at 3432.84cm -1 A superimposed stretching vibration peak of Si-OH groups appears at the position; a large number of Si-OH groups are bonded to metal ions (La 3+ ,Eu 3+ ) LaVO formation on HHSS surface 4 :Eu 3+ Plays an important role; located at 1633.83cm -1 Is of physical adsorption H 2 O-OH vibration. 1079.3cm -1 、960.53cm -1 、800.66cm -1 And 459.04cm -1 Si-O-Si stretching of HHSS band; in LaVO 4 :Eu 3+ The fluorescent powder is positioned at 445.76cm -1 Is characterized by VO 4 3- Vibration at 778.11cm -1 VO of (2) 4 3- The V-O bond of the group is determined; at HHSS@LaVO 4 ：Eu 3+ In the FTIR spectrum of the phosphor, at 822.55cm -1 Where V-O is covered with Si-O-Si at 446.13cm -1 VO at 4 3- And Si-O-Si overlap. HHSS@LaVO after annealing at 800 DEG C 4 :Eu 3+ HHSS formed in phosphorThe signal of Si-OH groups is considerably reduced. These results are consistent with those of XRD, further demonstrating the formation of LaVO on the HHSS surface 4 :Eu 3 + And (3) nanoparticles.
FIG. 3 shows (c) HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Composite nano fluorescent powder and (a) HHSS-OH and (b) LaVO prepared by comparative example 4 :Eu 3+ SEM images of (a). As can be seen from the figure, HHSS-OH consisted of ordered packing of small hollow silica nanospheres (-10 nm) to form large hollow spheres with average particle size-100 nm (FIG. 3 a); tetragonal LaVO 4 :Eu 3+ The particle size was about 25nm, and significant agglomeration occurred after annealing (FIG. 3 b); by loading LaVO 4 :Eu 3+ HHSS@LaVO formed after nanoparticles 4 :Eu 3+ The phosphor retained the morphology of the HHSS (fig. 3 c).
FIG. 4 shows (c) HHSS@LaVO prepared in example 3 of the present application 4 :Eu 3+ Composite nano fluorescent powder and (a) HHSS-OH and (b) LaVO prepared by comparative example 4 :Eu 3+ HRTEM images of (a). HRTEM images of HHSS-OH can more clearly observe their nanolayered cavity structure (fig. 4 a); tetragonal LaVO 4 :Eu 3+ The grain size is about 25nm, obvious agglomeration phenomenon appears after annealing, the lattice stripes are clear, and the lattice spacing is(FIG. 4 b); HHSS@LaVO 4 :Eu 3+ HRTEM image of phosphor shows ultra-small LaVO with size of about 2nm 4 :Eu 3+ The nanoislands are embedded on the HHSS (fig. 4C). The spacing between adjacent lattice fringes is aboutCorresponds to t-LaVO 4 The (200) crystal plane of (C) is consistent with the XRD characterization result.
FIG. 5 shows HHSS@LaVO prepared in example 3 4 :Eu 3+ Preparation of HHSS-OH N by composite nano fluorescent powder and comparative example 2 Adsorption-desorption curves. From the figure, it can be seen that LaVO is loaded 4 :Eu 3+ Obtained after thatHHSS@LaVO 4 :Eu 3+ The specific surface area of the composite nano fluorescent powder relative to HHSS-OH is not obviously reduced, and is only 597.21m 2 The/g drops to 584.94m 2 G, as demonstrated by XRD, FTIR, SEM and HRTEM characterizations, supra.
FIG. 6 is a sample of HHSS@LaVO prepared in example 3 4 :Eu 3+ Excitation-emission spectrum of the composite nano fluorescent powder. A broad and strong band at 240-350 nm due to VO 4 3- And VO (Voice over Internet protocol) 4 3- →Eu 3+ O-V charge transfer in energy transfer; emission spectra excited at 300nm showed emission from Eu 3+ Five sets of emission lines for ions, centered at 538, 594, 618, 651 and 700 nm. The entire excitation-emission process under uv radiation is divided into three main steps: first, the ultraviolet radiation is VO 4 3- Group absorption; then, the excited energy is transferred to Eu 3+ Exciting ions; finally, eu 3+ The ions emit back to the ground state and release photons.
FIG. 7 is a sample of HHSS@LaVO prepared in example 3 4 :Eu 3+ The composite nano fluorescent powder is dispersed in aqueous solution to form the emission spectra of colloidal solutions with different concentrations. As can be seen from the graph, the fluorescence intensity is dependent on HHSS@LaVO 4 :Eu 3+ The concentration is reduced, the linear fitting coefficient reaches 0.999, which shows that the fluorescence intensity of the colloidal solution has strong linear correlation with the concentration thereof.
FIG. 8 is a HHSS@LaVO prepared in example 3 4 :Eu 3+ And the composite nano fluorescent powder is dispersed in an aqueous solution to form an emission spectrum of a colloidal solution (20 mg/L). From the figure, HHSS@LaVO 4 :Eu 3+ The colloidal solution has better stability under both acidic and neutral conditions, and the fluorescence intensity of the solution slightly increases with the increase of pH under alkaline conditions.
FIG. 9 is a sample of HHSS@LaVO prepared in example 3 4 :Eu 3+ The stability of a colloidal solution (20 mg/L) formed by dispersing the composite nano-phosphor in an aqueous solution was tested for emission spectrum. The emission spectrum of the solution is hardly weakened after the solution is placed in a room in a sealing way for 60 days, which shows that the prepared HHSS@LaVO 4 :Eu 3+ The colloidal solution has good stability.
FIG. 10 shows HHSS@LaVO prepared in example 3 and comparative example 4 :Eu 3+ Composite nano fluorescent powder and LaVO 4 :Eu 3+ Emission spectrum of a solution formed by dispersing the phosphor in an aqueous solution. LaVO in two solutions 4 :Eu 3+ The effective concentration of (a total concentration of the former is 40mg/L and a total concentration of the latter is 8 mg/L) is the same as that of LaVO 4 :Eu 3+ Solution HHSS@LaVO 4 :Eu 3+ The fluorescence intensity of the colloidal solution is enhanced by 5 times.
The inventors also prepared HHSS@LaVO for other examples 4 :Eu 3+ The composite nano-phosphor was subjected to the experimental tests and analyses described above with reference to fig. 1-10, and the results obtained were comparable to the test and analysis results described above.
Claims (10)
1. A red light emission silicon-based rare earth composite nano fluorescent powder is characterized in that: uses the hollow silicon dioxide sphere HHSS-OH with activated surface hydroxyl as a carrier, and uses the surface hydroxyl and LaVO thereof 4 :Eu 3+ Coordination of LaVO 4 :Eu 3+ The nano particles are anchored on the surface of HHSS, and HHSS@LaVO is obtained after annealing 4 :Eu 3+ Composite nano fluorescent powder; the LaVO 4 :Eu 3+ Is Eu 3+ Doped LaVO 4 Within the lattice.
2. The red light emitting silicon-based rare earth composite nano-phosphor according to claim 1, wherein: hollow silica sphere HHSS-OH and LaVO with surface hydroxyl activated 4 :Eu 3+ Mixing the precursor solutions, stirring to form a suspension, performing hydrothermal reaction, centrifuging to collect solid, drying, and annealing to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
3. The red light emitting silicon-based rare earth composite nano-phosphor according to claim 1, wherein: and (3) refluxing and stirring the silica spheres in a mixed solution of hydrochloric acid and ethanol to remove CTAB templates in the mixed solution, so as to obtain the hollow silica spheres HHSS-OH with surface hydroxyl groups activated.
4. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to any one of claims 1 to 3, which is characterized in that: the method comprises the following steps:
(1) Adding silicon dioxide balls into absolute ethyl alcohol, adding hydrochloric acid solution after ultrasonic stirring, refluxing and stirring under the oil bath condition, cooling, filtering and washing, collecting solid, and drying to obtain HHSS-OH with surface hydroxyl activation as a product A;
(2) Adding the product A into absolute ethyl alcohol, ultrasonically stirring, adding deionized water, and ultrasonically stirring again to obtain milky suspension, wherein the milky suspension is the product B;
(3) La (NO) 3 ) 3 ·6H 2 Adding O into deionized water, stirring, and adding Eu (NO) 3 ) 3 ·6H 2 O, stirring to obtain a transparent La-Eu solution which is a C product;
(4) NH is added to 4 VO 3 Adding into deionized water, heating, stirring, dissolving, and cooling to room temperature to obtain NH 4 VO 3 The solution is D;
(5) Adding the product C into the product B, ultrasonically stirring, adding the product D, and continuously ultrasonically stirring to obtain a mixed solution which is the product E;
(6) Carrying out hydrothermal reaction on the E product, cooling, filtering, washing, collecting solid, drying and annealing to obtain HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
5. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to claim 4, which is characterized in that: in the step (1), 0.8-1.2g of silica spheres are added into 100-140mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 20-40min, 220-260 mu L of hydrochloric acid solution is added, the mass fraction of the hydrochloric acid solution is 36-38%, reflux stirring is carried out for 4-6h under the oil bath condition of 70-90 ℃, cooling is carried out to 20-30 ℃, filtering and washing are carried out, the solid is collected, and drying is carried out for 8-12h at 70-90 ℃, thus obtaining the hollow silica HHSS-OH with surface hydroxyl activation, which is A product.
6. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to claim 4, which is characterized in that: in the step (2), 0.3-0.5g of A product is added into 4-8mL of absolute ethyl alcohol, ultrasonic stirring is carried out for 20-40min, 30-38mL of deionized water is added, ultrasonic stirring is carried out for 4-6h, and suspension is obtained as B product.
7. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to claim 4, which is characterized in that: in the step (3), 0.10 to 0.15. 0.15gLa (NO) 3 ) 3 ·6H 2 Adding O into 15-25mL deionized water, stirring, and adding 0.01-0.02-gEu (NO) 3 ) 3 ·6H 2 And O, stirring to obtain La-Eu solution which is a C product.
8. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to claim 4, which is characterized in that: in the step (4), 0.03 to 0.05 and gNH are added 4 VO 3 Adding into 15-25mL deionized water, heating at 50-70deg.C, stirring for dissolving, and cooling to 20-30deg.C to obtain NH 4 VO 3 The solution is D product.
9. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to claim 4, which is characterized in that: in the step (5), 15-20mLC products are added into 34-46mLB products, ultrasonic stirring is carried out for 20-40min, 15-25mLD products are added into the mixture, ultrasonic stirring is continued for 20-40min, and the mixture is obtained as E products.
10. The method for preparing the red light emitting silicon-based rare earth composite nano fluorescent powder according to claim 4, which is characterized in that: in the step (6), the E product is subjected to hydrothermal reaction at 100-120 ℃ for 10-12h, cooled to 15-30 ℃, filtered and washed, solid is collected, dried at 70-90 ℃ for 8-12h, and the annealing process is that the E product is heated to 700-900 ℃ at a heating rate of 4-10 ℃/min, baked for 5-7h and naturally cooled, thus obtaining HHSS@LaVO 4 :Eu 3+ And (3) compounding nano fluorescent powder.
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